Method for purifying synthetic mesoporous crystalline material

ABSTRACT

A method is described for purifying an ultra-large pore crystalline material by contact with an aqueous solution having a hydroxyl concentration sufficient to solubilize an impurity phase but not the crystalline material. The purified crystalline material is also described, as is a hydrocarbon conversion process over the purified crystalline material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 625,245 filed Dec. 10, 1990, which was a continuation-in-partof application Ser. No. 470,008, filed Jan. 25, 1990.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a method for purifying a novel composition ofsynthetic ultra-large pore crystalline material by solubilizing animpurity phase.

2. Description of the Prior Art

Porous inorganic solids have found great utility as catalysts andseparations media for industrial application. The openness of theirmicrostructure allows molecules access to the relatively large surfaceareas of these materials that enhance their catalytic and sorptiveactivity. The porous materials in use today can be sorted into threebroad categories using the details of their microstructure as a basisfor classification. These categories are the amorphous andparacrystalline supports, the crystalline molecular sieves and modifiedlayered materials. The detailed differences in the microstructures ofthese materials manifest themselves as important differences in thecatalytic and sorptive behavior of the materials, as well as indifferences in various observable properties used to characterize them,such as their surface area, the sizes of pores and the variability inthose sizes, the presence or absence of X-ray diffraction patterns andthe details in such patterns, and the appearance of the materials whentheir microstructure is studied by transmission electron microscopy andelectron diffraction methods.

Amorphous and paracrystalline materials represent an important class ofporous inorganic solids that have been used for many years in industrialapplications. Typical examples of these materials are the amorphoussilicas commonly used in catalyst formulations and the paracrystallinetransitional aluminas used as solid acid catalysts and petroleumreforming catalyst supports. The term "amorphous" is used here toindicate a material with no long range order and can be somewhatmisleading, since almost all materials are ordered to some degree, atleast on the local scale. An alternate term that has been used todescribed these materials is "X-ray indifferent". The microstructure ofthe silicas consists of 100-250 Angstrom particles of dense amorphoussilica (Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition,Vol. 20, John Wiley & Sons, New York, p. 766-781, 1982), with theporosity resulting from voids between the particles. Since there is nolong range order in these materials, the pore sizes tend to bedistributed over a rather large range. This lack of order also manifestsitself in the X-ray diffraction pattern, which is usually featureless.

Paracrystalline materials such as the transitional aluminas also have awide distribution of pore sizes, but better defined X-ray diffractionpatterns usually consisting of a few broad peaks. The microstructure ofthese materials consists of tiny crystalline regions of condensedalumina phases and the porosity of the materials results from irregularvoids between these regions (K. Wefers and Chanakya Misra, "Oxides andHydroxides of Aluminum", Technical Paper No. 19 Revised, Alcoa ResearchLaboratories, p. 54-59, 1987). Since, in the case of either material,there is no long range order controlling the sizes of pores in thematerial, the variability in pore size is typically quite high. Thesizes of pores in these materials fall into a regime called themesoporous range, which, for the purposes of this application, is fromabout 13 to 200 Angstroms.

In sharp contrast to these structurally ill-defined solids are materialswhose pore size distribution is very narrow because it is controlled bythe precisely repeating crystalline nature of the materials,microstructure. These materials are called "molecular sieves", the mostimportant examples of which are zeolites.

Zeolites, both natural and synthetic, have been demonstrated in the pastto have catalytic properties for various types of hydrocarbonconversion. Certain zeolitic materials are ordered, porous crystallinealuminosilicates having a definite crystalline structure as determinedby X-ray diffraction, within which there are a large number of smallercavities which may be interconnected by a number of still smallerchannels or pores. These cavities and pores are uniform in size within aspecific zeolite material. Since the dimensions of these pores are suchas to accept for adsorption molecules of certain dimensions whilerejecting those of larger dimensions, these materials are known as"molecular sieves" and are utilized in a variety of ways to takeadvantage of these properties.

Such molecular sieves, both natural and synthetic, include a widevariety of positive ion-containing crystalline silicates. Thesesilicates can be described as a rigid three-dimensional framework ofSiO₄ and Periodic Table Group IIIB element oxide, e.g. AlO₄, in whichthe tetrahedra are cross-linked by the sharing of oxygen atoms wherebythe ratio of the total Group IIIB element, e.g. aluminum, and Group IVBelement, e.g. silicon, atoms to oxygen atoms is 1:2. The electrovalenceof the tetrahedra containing the Group IIIB element, e.g. aluminum, isbalanced by the inclusion in the crystal of a cation, for example, analkali metal or an alkaline earth metal cation. This can be expressedwherein the ratio of the Group IIIB element, e.g. aluminum, to thenumber of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal tounity. One type of cation may be exchanged either entirely or partiallywith another type of cation utilizing ion exchange techniques in aconventional manner. By means of such cation exchange, it has beenpossible to vary the properties of a given silicate by suitableselection of the cation. The spaces between the tetrahedra are occupiedby molecules of water prior to dehydration.

Prior art techniques have resulted in the formation of a great varietyof synthetic zeolites. Many of these zeolites have come to be designatedby letter or other convenient symbols, as illustrated by zeolite A (U.S.Pat. No. 2,882,243); zeolite X (U.S. Pat. No. 2,882,244); zeolite Y(U.S. Pat. No. 3,130,007); zeolite ZK-5 (U.S. Pat. No. 3,247,195);zeolite ZK-4 (U.S. Pat. No. 3,314,752); zeolite ZSM-5 (U.S. Pat. No.3,702,886); zeolite ZSM-11 (U.S. Pat. No. 3,709,979); zeolite ZSM-12(U.S. Pat. No. 3,832,449); zeolite ZSM-20 (U.S. Pat. No. 3,972,983);ZSM-35 (U.S. Pat. No. 4,016,245); and zeolite ZSM-23 (U.S. Pat. No.4,076,842), merely to name a few.

The SiO₂ /Al₂ O₃ ratio of a given zeolite is often variable. Forexample, zeolite X can be synthesized with SiO₂ /Al₂ O₃ ratios of from 2to 3; zeolite Y, from 3 to about 6. In some zeolites, the upper limit ofthe SiO₂ /Al₂ O₃ ratio is unbounded. ZSM-5 is one such example whereinthe SiO₂ /Al₂ O₃ ratio is at least 5 and up to the limits of presentanalytical measurement techniques. U.S. Pat. No. 3,941,871 (Re. 29,948)discloses a porous crystalline silicate made from a reaction mixturecontaining no deliberately added alumina in the recipe and exhibitingthe X-ray diffraction pattern characteristic of ZSM-5. U.S. Pat. Nos.4,061,724; 4,073,865 and 4,104,294 describe crystalline silicate ofvarying alumina and metal content.

Aluminum phosphates are taught in the U.S. Pat. Nos. 4,310,440 and4,385,994, for example. These aluminum phosphate materials haveessentially electroneutral lattices. U.S. Pat. No. 3,801,704 teaches analuminum phosphate treated in a certain way to impart acidity.

An early reference to a hydrated aluminum phosphate which is crystallineuntil heated at about 110° C., at which point it becomes amorphous ortransforms, is the "H₁ " phase or hydrate of aluminum phosphate ofF.d'Yvoire, Memoir Presented to the Chemical Society, No. 392, "Study ofAluminum Phosphate and Trivalent Iron", July 6, 1961 (received), pp.1762-1776. This material, when crystalline, is identified by the JCPDSInternational Center for Diffraction Data card number 15-274. Onceheated at about 110° C., however, the d'Yvoire material becomesamorphous or transforms to the aluminophosphate form of tridymite.

Compositions comprising crystals having a framework topology afterheating at 110° C. or higher giving an X-ray diffraction patternconsistent with a material having pore windows formed by 18 tetrahedralmembers of about 12-13 Angstroms in diameter are taught in U.S. Pat. No.4,880,611.

A naturally occurring, highly hydrated basic ferric oxyphosphatemineral, cacoxenite, is reported by Moore and Shen, Nature,Vol. 306, No.5941, pp. 356-358 (1983) to have a framework structure containing verylarge channels with a calculated free pore diameter of 14.2 Angstroms.R. Szostak et al., Zeolites: Facts, Figures, Future, Elsevier SciencePublishers B.V., 1989, present work showing cacoxenite as being veryhydrophilic, i.e. adsorbing non-polar hydrocarbons only with greatdifficulty. Their work also shows that thermal treatment of cacoxenitecauses an overall decline in X-ray peak intensity.

Silicoaluminophosphates of various structures are taught in U.S. Pat.No. 4,440,871. Aluminosilicates containing phosphorous, i.e.silicoaluminophosphates of particular structures are taught in U.S. Pat.Nos. 3,355,246 (i.e. ZK-21) and 3,791,964 (i.e. ZK-22). Other teachingsof silicoaluminophosphates and their synthesis include U.S. Pat. Nos.4,673,559 (two-phase synthesis method); 4,623,527 (MCM-10); 4,639,358(MCM-1); 4,647,442 (MCM-2); 4,664,897 (MCM-4); 4,638,357 (MCM-5); and4,632,811 (MCM-3).

A method for synthesizing crystalline metalloaluminophosphates is shownin U.S. Pat. No. 4,713,227, and an antimonophosphoaluminate and themethod for its synthesis are taught in U.S. Pat. No. 4,619,818. U.S.Pat. No. 4,567,029 teaches metalloaluminophosphates, andtitaniumaluminophosphate and the method for its synthesis are taught inU.S. Pat. No. 4,500,651.

The phosphorus-substituted zeolites of Canadian Patents 911,416;911,417; and 911,418 are referred to as "aluminosilicophosphate"zeolites. Some of the phosphorus therein appears to be occluded, notstructural.

U.S. Pat. No. 4,363,748 describes a combination of silica andaluminum-calcium-cerium phosphate as a low acid activity catalyst foroxidative dehydrogenation. Great Britain Patent 2,068,253 discloses acombination of silica and aluminum-calcium-tungsten phosphate as a lowacid activity catalyst for oxidative dehydrogenation. U.S. Pat. No.4,228,036 teaches an alumina-aluminum phosphate-silica matrix as anamorphous body to be mixed with zeolite for use as cracking catalyst.U.S. Pat. No. 3,213,035 teaches improving hardness of aluminosilicatecatalysts by treatment with phosphoric acid. The catalysts areamorphous.

Other patents teaching aluminum phosphates include U.S. Pat. Nos.4,365,095; 4,361,705; 4,222,896; 4,210,560; 4,179,358; 4,158,621;4,071,471; 4,014,945; 3,904,550; and 3,697,550.

The precise crystalline microstructure of most zeolites manifests itselfin a well-defined X-ray diffraction pattern that usually contains manysharp maxima and that serves to uniquely define the material. Similarly,the dimensions of pores in these materials are very regular, due to theprecise repetition of the crystalline microstructure. All molecularsieves discovered to date have pore sizes in the microporous range,which is usually quoted as 2 to 20 Angstroms, with the largest reportedbeing about 12 Angstroms.

Certain layered materials, which contain layers capable of being spacedapart with a swelling agent, may be pillared to provide materials havinga large degree of porosity. Examples of such layered materials includeclays. Such clays may be swollen with water, whereby the layers of theclay are spaced apart by water molecules. Other layered materials arenot swellable with water, but may be swollen with certain organicswelling agents such as amines and quaternary ammonium compounds.Examples of such non-water swellable layered materials are described inU.S. Pat. No. 4,859,648 and include layered silicates, magadiite,kenyaite, trititanates and perovskites. Another example of a non-waterswellable layered material, which can be swollen with certain organicswelling agents, is a vacancy-containing titanometallate material, asdescribed in U.S. Pat. No. 4,831,006.

Once a layered material is swollen, the material may be pillared byinterposing a thermally stable substance, such as silica, between thespaced apart layers. The aforementioned U.S. Pat. Nos. 4,831,006 and4,859,648 describe methods for pillaring the non-water swellable layeredmaterials described therein and are incorporated herein by reference fordefinition of pillaring and pillared materials.

Other patents teaching pillaring of layered materials and the pillaredproducts include U.S. Pat. Nos. 4,216,188; 4,248,739; 4,176,090; and4,367,163; and European Patent Application 205,711.

The X-ray diffraction patterns of pillared layered materials can varyconsiderably, depending on the degree that swelling and pillaringdisrupt the otherwise usually well-ordered layered microstructure. Theregularity of the microstructure in some pillared layered materials isso badly disrupted that only one peak in the low angle region on theX-ray diffraction pattern is observed, at a d-spacing corresponding tothe interlayer repeat in the pillared material. Less disrupted materialsmay show several peaks in this region that are generally orders of thisfundamental repeat. X-ray reflections from the crystalline structure ofthe layers are also sometimes observed. The pore size distribution inthese pillared layered materials is narrower than those in amorphous andparacrystalline materials but broader than that in crystalline frameworkmaterials.

Applicants know of no prior art teaching the ultra-large porenon-layered crystalline materials of the present invention.

These crystalline materials of the invention exhibit, after calcination,an X-ray diffraction pattern with at least one peak at a d-spacinggreater than about 18 Angstrom Units. In a preferred embodiment, thematerial gives X-ray diffraction patterns with at least two peaks, wherethe d-spacing of the second peak is greater than one half the d-spacingof the first peak. It has been observed that many of these materialsshow an asymmetric first peak which appears to be another phase in theproduct.

Methods for crystallization of molecular sieve material have, ingeneral, included calcination of the synthesized material to removeadsorbed water and organic material remaining within the synthesizedmolecular sieve. In the present ultra-large pore crystalline material,however, an impurity peak may remain even after calcination.

U.S. Pat. No. 5,001,094 describes removing carbonaceous material fromthe surfaces of regenerated, coked zeolite by contacting with an aqueoussolution of alkali metal or alkaline earth metal carbonate to restorecatalyst activity. The present crystalline material differs frompreviously known crystalline molecular sieve materials such as zeolitesand the present material is treated for the removal of an impurity phasewhich occurs in the as-synthesized crystalline material. One cannotpredict reactions in this new material based on reactions in previouslyknown molecular sieves because of the chemical differences.

It is therefore an object of the invention to purify the novel ultralarge pore crystalline material described herein.

It is also an object of the invention to enhance the activity,absorption and diffusion properties of the novel crystalline material.

SUMMARY OF THE INVENTION

Accordingly, there is provided a method for purifying a composition ofmatter. The composition of matter comprises an inorganic, porous,non-layered crystalline phase material exhibiting, after calcination, anX-ray diffraction pattern with at least one peak at a d-spacing greaterthan about 18 Angstrom Units and having a benzene adsorption capacity ofgreater than 15 grams benzene per 100 grams of said material at 50 torrand 25° C. and containing an impurity phase. In the method of theinvention, the crystalline material is contacted with an aqueoussolution having an OH concentration sufficient to solubilize theimpurity phase but not the crystalline phase material.

In a preferred embodiment, the composition of matter comprises aninorganic, porous crystalline phase material having a hexagonalarrangement of uniformly-sized pores at least about 13 Angstromsdiameter and exhibiting, after calcination, a hexagonal electrondiffraction pattern that can be indexed with a d₁₀₀ value greater than18 Angstrom Units.

Advantageously, the crystalline phase material treated according to theinvention gives a crystalline product with higher quality. Furthermore,X-ray diffraction patterns show that the treated product gives increasedintensity of the desired crystalline phase material and decreasedintensity of impurity phase. Improved quality product leads to enhancedactivity adsorption and diffusion properties.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1a is an X-ray diffraction pattern of the untreated product ofExample 1;

FIG. 1b is an X-ray diffraction of the treated product of Example 2;

FIG. 2a is an X-ray diffraction pattern of the untreated product ofExample 3;

FIG. 2b is an X-ray diffraction pattern of the treated product ofExample 4;

FIG. 3a is an X-ray diffraction pattern of the untreated product ofExample 5;

FIG. 3b is an X-ray diffraction pattern of the treated product ofExample 6.

DETAILED DESCRIPTION OF THE INVENTION

In the purification method of the invention, the as-synthesizedcrystalline material is contacted with an aqueous treating solutionhaving a concentration of hydroxyls sufficient to solubilize theimpurity phase.

Useful as treating agents are aqueous solutions of alkalies. Generally,aqueous solutions of alkalies are high in hydroxyl ions and have a pHabove about 7. An alkali is any compound having highly basic propertiesand having the ability to neutralize acids. Caustic alkali solutionsinclude sodium hydroxide, potassium hydroxide and the milder alkaliesinclude the carbonates of alkali or alkaline earth metals includingsodium carbonate, potassium carbonate, as well as the carbonates oflithium, rubidium and cesium; also calcium, magnesium, strontium andbarium. The preferred aqueous solutions have a pH greater than about 8and include carbonates of sodium and potassium. The molality of thecarbonates in aqueous solution will, of course, be related to theeffective hydroxyl concentration of the aqueous solution. The molalityof the carbonate may be from about 0.001 to about 1 M, preferably fromabout 0.1 to about 0.5 M.

The crystalline material is contacted with the treatment solution for aperiod of time to solubilize impurities. The amount of treatmentsolution used is sufficient to saturate the crystalline material.Preferably, the amount of aqueous solution is sufficient to thoroughlysoak the crystalline material. The treatment conditions may berelatively mild, for example at a temperature of from about 25° to about100° C., preferably from about 50° to about 80° C., for a time ranging,for example, from about 15 minutes to about 2 hours. Following thesolubilization of the impurities, the treated material may be filtered,washed and calcined.

Material treated according to the invention shows an improved catalyticactivity in hydrocarbon conversion processes, for example, inalkylation. Aromatic hydrocarbons can be alkylated by reaction with anolefin in the presence of the treated catalytic crystalline material.For the alkylation process of this invention, the crystalline materialcan be employed in combination with a support or binder as describedbelow.

Hydrocarbons which may be alkylated by the process of the invention arearomatic compounds such as benzenes, naphthalenes, anthracenes, and thelike and substituted derivatives thereof; and alkyl substitutedaromatics, e.g. toluene, xylene, and homologs thereof. In addition,other non-polar substituent groups may also be attached to the aromaticring including, by way of example:

Methyl (--CH₃)

Ethyl (--C₂ H₅)

Tert-butyl (--C(CH₃)₃)

Alkyl (--C_(n) H.sub.(2n+1))

Cycloalkyl (C_(n) H.sub.(2n+1))

Phenyl (C₆ H₅)

Naphthyl (C₁₀ H₇)and

Aryl (any aromatic radical)

In accordance with this invention, the preferred alkylating agents areC₂ to C₂₀ olefins such as ethylene, propylene, dodecylene, as well asformaldehyde, alkyl halides and alcohols; the alkyl portion thereofhaving from 1 to 24 carbon atoms. Numerous other acyclic compoundshaving at least one reactive alkyl radical may be utilized as alkylatingagents. Alkylation may be conducted at about 340° to 490° C. WHSV=28hr⁻¹, 25-450 psig with benzene to ethylene mole ratio of about 1-60.

The process of the present invention comprises contacting a hydrocarboncharge in a reaction zone with an alkylating agent under alkylationconditions in the presence of catalyst. Operating conditions employed inthe process of the present invention are dependent, at least in part, onthe specific alkylation reaction being effected. Such conditions astemperature, pressure, space velocity and molar ratio of the reactantsand the presence of inert diluents will have some effect on the process.

As demonstrated hereinafter, the inorganic, non-layered mesoporouscrystalline material of this invention has the following composition:

    M.sub.n/q (W.sub.a X.sub.b Y.sub.c Z.sub.d O.sub.h)

wherein W is a divalent element, such as a divalent first row transitionmetal, e.g. manganese, cobalt and iron, and/or magnesium, preferablycobalt; X is a trivalent element, such as aluminum, boron, iron and/orgallium, preferably aluminum; Y is a tetravalent element such as siliconand/or germanium, preferably silicon; Z is a pentavalent element, suchas phosphorus; M is one or more ions, such as, for example, ammonium,Group IA, IIA and VIIB ions, usually hydrogen, sodium and/or fluorideions; n is the charge of the composition excluding M expressed asoxides; q is the weighted molar average valence of M; n/q is the numberof moles or mole fraction of M; a, b, c and d are mole fractions of W,X, Y and Z, respectively; h is a number of from 1 to 2.5; and (a+b+c+d)=1.

A preferred embodiment of the above crystalline material is when (a+b+c)is greater than d, and h=2. A further embodiment is when a and d=0, andh=2.

In the as-synthesized form, the material of this invention has acomposition, on an anhydrous basis, expressed empirically as follows:

    rRM.sub.n/q (W.sub.a X.sub.b Y.sub.c Z.sub.d O.sub.h)

wherein R is the total organic material not included in M as an ion, andr is the coefficient for R, i.e. the number of moles or mole fraction ofR.

The M and R components are associated with the material as a result oftheir presence during crystallization, and are easily removed or, in thecase of M, replaced by post-crystallization methods hereinafter moreparticularly described.

To the extent desired, the original M, e.g. sodium ions of theas-synthesized material of this invention can be replaced in accordancewith techniques well known in the art, at least in part, by ion exchangewith other ions. Preferred replacement ions include metal ions, hydrogenions, hydrogen precursor, e.g. ammonium, ions and mixtures thereof.Particularly preferred ions are those which tailor the catalyticactivity for certain hydrocarbon conversion reactions. These includehydrogen, rare earth metals and metals of Group IA (e.g. K), IIA (e.g.Ca), VIIA (e.g. Mn), VIIIA (e.g. Ni), IB (e.g. Cu), IIB (e.g. Zn), IIIB(e.g. In), IVB (e.g. Sn), and VIIB (e.g. F) of the Periodic Table of theElements (Sargent-Welch Scientific Co. Cat. No. S-18806, 1979) andmixtures thereof.

The crystalline (i.e. meant here as having sufficient order to provide adiffraction pattern such as, for example, by X-ray, electron or neutrondiffraction, following calcination with at least one peak) mesoporousmaterial of this invention may be characterized by its heretoforeunknown structure, including extremely large pore windows, and highsorption capacity. The term "mesoporous" is used here to indicatecrystals having uniform pores within the range of at least about 13Angstroms or from about 13 Angstroms to about 200 Angstroms. Thematerials of this invention will have uniform pores within the range offrom about 13 Angstroms to about 200 Angstroms, more usually from about15 Angstroms to about 100 Angstroms. For the purposes of thisapplication, a working definition of "porous" is a material that adsorbsat least 1 gram of a small molecule, such as Ar, N₂, n-hexane orcyclohexane, per 100 grams of the solid.

The material of the present invention can be distinguished from otherporous inorganic solids by the regularity of its large open pores, whosepore size more nearly resembles that of amorphous or paracrystallinematerials, but whose regular arrangement and uniformity of size (poresize distribution within a single phase of, for example, ± 25%, usually± 15% or less of the average pore size of that phase) resemble morethose of crystalline framework materials such as zeolites. In one formthe material appears to have a hexagonal arrangement of large channelsthat can be synthesized with open internal diameters from about 13Angstroms to about 200 Angstroms. The term "hexagonal" is intended toencompass not only materials that exhibit mathematically perfecthexagonal symmetry within the limits of experimental measurement, butalso those with significant observable deviations from that ideal state.A working definition as applied to the microstructure of the presentinvention would be that most channels in the material would besurrounded by six nearest neighbor channels at roughly the samedistance. Defects and imperfections will cause significant numbers ofchannels to violate this criterion to varying degrees, depending on thequality of the material's preparation. Samples which exhibit as much as± 25% random deviation from the average repeat distance between adjacentchannels still clearly give recognizable images of the presentultra-large pore materials. Comparable variations are also observed inthe d₁₀₀ values from the electron diffraction patterns.

The most regular preparations of the material of the present inventiongive an X-ray diffraction pattern with a few distinct maxima in theextreme low angle region. The positions of these peaks approximately fitthe positions of the hkO reflections from a hexagonal lattice. The X-raydiffraction pattern, however, is not always a sufficient indicator ofthe presence of these materials, as the degree of regularity in themicrostructure and the extent of repetition of the structure withinindividual particles affect the number of peaks that will be observed.Indeed, preparations with only one distinct peak in the low angle regionof the X-ray diffraction pattern have been found to contain substantialamounts of the material in them. Other techniques to illustrate themicrostructure of this material are transmission electron microscopy andelectron diffraction. Properly oriented specimens of the material show ahexagonal arrangement of large channels and the corresponding electrondiffraction pattern gives an approximately hexagonal arrangement ofdiffraction maxima. The d₁₀₀ spacing of the electron diffractionpatterns is the distance between adjacent spots on the hkO projection ofthe hexagonal lattice and is related to the repeat distance a₀ betweenchannels observed in the electron micrographs through the formula d₁₀₀=a₀ √3/2. This d₁₀₀ spacing observed in the electron diffractionpatterns corresponds to the d-spacing of a low angle peak in the X-raydiffraction pattern of the material. The most highly orderedpreparations of the material obtained so far have 20-40 distinct spotsobservable in the electron diffraction patterns. These patterns can beindexed with the hexagonal hkO subset of unique reflections of 100, 110,200, 210, etc., and their symmetry-related reflections.

In its calcined form, the crystalline material of the invention may befurther characterized by an X-ray diffraction pattern with at least onepeak at a position greater than about 18 Angstrom Units d-spacing (4.909degrees two-theta for Cu K-alpha radiation) which corresponds to thed₁₀₀ value of the electron diffraction pattern of the material, and anequilibrium benzene adsorption capacity of greater than about 15 gramsbenzene/100 grams crystal at 50 torr and 25° C. This sorption is basedon the assumption that the crystal material has been treated ifnecessary in an attempt to insure no pore blockage by incidentalcontaminants.

The equilibrium benzene adsorption capacity characteristic of thismaterial is measured on the basis of no pore blockage by incidentalcontaminants. For instance, the sorption test will be conducted on thecrystalline material phase having any pore blockage contaminants andwater removed by ordinary methods. Water may be removed by dehydrationtechniques, e.g. thermal treatment. Pore blocking inorganic amorphousmaterials. e.g. silica, and organics may be removed by contact with acidor base or other chemical agents such that the detrital material will beremoved without detrimental effect on the crystal of the invention.

More particularly, the calcined crystalline non-layered material of theinvention may be characterized by an X-ray diffraction pattern with atleast two peaks at positions greater than about 10 Angstrom Unitsd-spacing (8.842 degrees two-theta for Cu K-alpha radiation), at leastone of which is at a position greater than about 18 Angstrom Unitsd-spacing, and no peaks at positions less than about 10 Angstrom unitsd-spacing with relative intensity greater than about 20% of thestrongest peak. Still more particularly, the X-ray diffraction patternof the calcined material of this invention will have no peaks atpositions less than about 10 Angstrom units d-spacing with relativeintensity greater than about 10% of the strongest peak. In any event, atleast one peak in the X-ray diffraction pattern will have a d-spacingthat corresponds to the d₁₀₀ value of the electron diffraction patternof the material.

Still more particularly, the calcined inorganic, non-layered crystallinematerial of the invention is characterized as having a pore size ofabout 13 Angstroms or greater as measured by physisorption measurements,hereinafter more particularly set forth. Pore size is considered amaximum perpendicular cross-section pore dimension of the crystal.

X-ray diffraction data were collected on a Scintag PAD X automateddiffraction system employing theta-theta geometry, Cu K-alpha radiation,and an energy dispersive X-ray detector. Use of the energy dispersiveX-ray detector eliminated the need for incident or diffracted beammonochromators. Both the incident and diffracted X-ray beams werecollimated by double slit incident and diffracted collimation systems.The slit sizes used, starting from the X-ray tube source, were 0.5, 1.0,0.3 and 0.2 mm, respectively. Different slit systems may producediffering intensities for the peaks. The materials of the presentinvention that have the largest pore sizes may require more highlycollimated incident X-ray beams in order to resolve the low angle peakfrom the transmitted incident X-ray beam.

The diffraction data were recorded by step-scanning at 0.04 degrees oftwo-theta, where theta is the Bragg angle, and a counting time of 10seconds for each step. The interplanar spacings, d's, were calculated inAngstrom units (A), and the relative intensities of the lines, I/I_(o),where I_(o) is one-hundredth of the intensity of the strongest line,above background, were derived with the use of a profile fittingroutine. The intensities were uncorrected for Lorentz and polarizationeffects. The relative intensities are given in terms of the symbolsvs=very strong (75-100), s=strong (50-74), m=medium (25-49) and w=weak(0-24). It should be understood that diffraction data listed as singlelines may consist of multipleoverlapping lines which under certainconditions, such as very high experimental resolution orcrystallographic changes, may appear as resolved or partially resolvedlines. Typically, crystallographic changes can include minor changes inunit cell parameters and/or a change in crystal symmetry, without asubstantial change in structure. These minor effects, including changesin relative intensities, can also occur as a result of differences incation content, framework composition, nature and degree of porefilling, thermal and/or hydrothermal history, and peak width/shapevariations due to particle size/shape effects, structural disorder orother factors known to those skilled in the art of X-ray diffraction.

The equilibrium benzene adsorption capacity is determined by contactingthe material of the invention, after dehydration or calcination at, forexample, about 450° C.-700° C. or about 540° C. for at least about onehour and other treatment, if necessary, in an attempt to remove any poreblocking contaminants, at 25° C. and 50 torr benzene until equilibriumis reached. The weight of benzene sorbed is then determined as moreparticularly described hereinafter.

When used as a sorbent or catalyst component, the composition of theinvention should be subjected to treatment to remove part or all of anyorganic constituent. The present composition can also be used as acatalyst component in intimate combination with a hydrogenatingcomponent such as tungsten, vanadium, molybdenum, rhenium, nickel,cobalt, chromium, manganese, or a noble metal such as platinum orpalladium or mixtures thereof where a hydrogenation-dehydrogenationfunction is to be performed. Such component can be in the composition byway of co-crystallization, exchanged into the composition to the extenta Group IIIB element, e.g. aluminum, is in the structure, impregnatedtherein or intimately physically admixed therewith. Such component canbe impregnated in or on to it such as, for example, by, in the case ofplatinum, treating the silicate with a solution containing a platinummetal-containing ion. Thus, suitable platinum compounds for this purposeinclude chloroplatinic acid, platinous chloride and various compoundscontaining the platinum amine complex.

The above crystalline material, especially in its metal, hydrogen andammonium forms can be beneficially converted to another form by thermaltreatment (calcination). This thermal treatment is generally performedby heating one of these forms at a temperature of at least 370° C. or400° C. for at least 1 minute and generally not longer than 20 hours,preferably from about 1 to about 10 hours. While subatmospheric pressurecan be employed for the thermal treatment, atmospheric pressure isdesired for reasons of convenience, such as in air, nitrogen, ammonia,etc. The thermal treatment can be performed at a temperature up to about925° C., or up to 750° C. with the hexagonal form. The thermally treatedproduct is particularly useful in the catalysis of certain hydrocarbonconversion reactions.

The crystalline material of this invention, when employed either as anadsorbent or as a catalyst component in an organic compound conversionprocess should be dehydrated, at least partially. This can be done byheating to a temperature in the range of 200° C. to 595° C. in anatmosphere such as air, nitrogen, etc. and at atmospheric,subatmospheric or superatmospheric pressures for between 30 minutes and48 hours. Dehydration can also be performed at room temperature merelyby placing the composition in a vacuum, but a longer time is required toobtain a sufficient amount of dehydration.

The usual method for synthesis of the ultra-large pore crystallinematerial involves preparation of a particular reaction mixturecomprising sources of alkali or alkaline earth metal cation, if desired,one or a combination of oxides selected from the group consisting ofdivalent element, trivalent element, tetravalent element and pentavalentelement, an organic directing agent and solvent or solvent mixture,maintaining said mixture under sufficient conditions of pH, temperatureand time for formation of said composition of matter, and recoveringsaid composition of matter. In this usual method, the organic directingagent is an ion of the formula R₁ R₂ R₃ R₄ Q⁺, wherein Q is nitrogen orphosphorus and wherein at least one of R₁, R₂, R₃ and R4 is aryl oralkyl of from 6 to about 36 carbon atoms or combinations thereof, theremainder of R₁, R₂, R₃ and R₄ being selected from the group consistingof hydrogen, alkyl of from 1 to 5 carbon atoms and combinations thereof.The compound from which the above organic directing agent ammonium orphosphonium ion is derived may be, for example, the hydroxide, halide,silicate or mixture thereof. The solvent or solvent mixture for use inthe usual method comprises a C₁ -C₆ alcohol, C₁ -C₆ diol, water ormixture thereof, with water preferred.

A first method involves a reaction mixture having an X₂ O₃ /YO₂ moleratio of from 0 to about 0.5, but an Al₂ O₃ /SiO₂ mole ratio of from 0to 0.01, a crystallization temperature of from about 25° C. to about250° C., preferably from about 50° C. to about 175° C., and an organicdirecting agent, hereinafter more particularly described, or, preferablya combination of that organic directing agent plus an additional organicdirecting agent, hereinafter more particularly described. This firstmethod comprises preparing a reaction mixture containing sources of, forexample, alkali or alkaline earth metal (M), e.g. sodium or potassium,cation if desired, one or a combination of oxides selected from thegroup consisting of divalent element W, e.g. cobalt, trivalent elementX, e.g. aluminum, tetravalent element Y, e.g. silicon, and pentavalentelement Z, e.g. phosphorus, an organic (R) directing agent, hereinaftermore particularly described, and a solvent or solvent mixture, such as,for example, C₁ -C₆ alcohols, C₁ -C₆ diols and/or water, especiallywater, said reaction mixture having a composition, in terms of moleratios of oxides, within the following ranges:

    ______________________________________                                        Reactants         Useful     Preferred                                        ______________________________________                                        X.sub.2 O.sub.3 /YO.sub.2                                                                         0 to 0.5 0.001 to 0.5                                     Al.sub.2 O.sub.3 /SiO.sub.2                                                                       0 to 0.01                                                                              0.001 to 0.01                                    X.sub.2 O.sub.3 /(YO.sub.2 + Z.sub.2 O.sub.5)                                                    0.1 to 100                                                                               0.1 to 20                                       X.sub.2 O.sub.3 /(YO.sub.2 + WO + Z.sub.2 O.sub.5)                                               0.1 to 100                                                                               0.1 to 20                                       Solvent/            1 to 1500                                                                                 5 to 1000                                     (YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3)                           OH.sup.- /YO.sub.2                                                                                0 to 10     0 to 5                                        (M.sub.2/e O + R.sub.2/f O)/                                                                    0.01 to 20  0.05 to 5                                       (YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3)                           M.sub.2/e O/        0 to 10     0 to 5                                        (YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub. 2 O.sub.3)                          R.sub.2/f O/      0.01 to 2.0                                                                               0.03 to 1.0                                     (YO.sub.2 WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3)                             ______________________________________                                    

wherein e and f are the weighted average valences of M and R,respectively.

In this first method, when no Z and/or W oxides are added to thereaction mixture, the pH is important and must be maintained at fromabout 9 to about 14. When Z and/or W oxides are present in the reactionmixture, the pH is not narrowly important for synthesis of the presentcrystalline material. In this, as well as the following methods forsynthesis of the present material the R₂ /_(f) O/(YO₂ +WO+Z₂ O₅ +X₂ O₃)ratio is important. When this ratio is less than 0.01 or greater than2.0, impurity products tend to be synthesized at the expense of thepresent material.

A second method for synthesis of the present crystalline materialinvolves a reaction mixture having an X₂ O₃ /YO₂ mole ratio of fromabout 0 to about 0.5, a crystallization temperature of from about 25° C.to about 250° C., preferably from about 50° C. to about 175° C., and twoseparate organic directing agents, i.e. the organic and additionalorganic directing agents, hereinafter more particularly described. Thissecond method comprises preparing a reaction mixture containing sourcesof, for example, alkali or alkaline earth metal (M), e.g. sodium orpotassium, cation if desired, one or a combination of oxides selectedfrom the group consisting of divalent element W, e.g. cobalt, trivalentelement X, e.g. aluminum, tetravalent element Y, e.g. silicon, andpentavalent element Z, e.g. phosphorus, a combination of organicdirecting agent and additional organic directing agent (R), eachhereinafter more particularly described, and solvent or solvent mixture,such as, for example, C₁ -C₆ alcohols, C₁ -C₆ diols and/or water,especially water, said reaction mixture having a composition, in termsof mole ratios of oxides, within the following ranges:

    ______________________________________                                        Reactants         Useful     Preferred                                        ______________________________________                                        X.sub.2 O.sub.3 /YO.sub.2                                                                         0 to 0.5 0.001 to 0.5                                     X.sub.2 O.sub.3 /(YO.sub.2 + Z.sub.2 O.sub.5)                                                    0.1 to 100                                                                               0.1 to 20                                       X.sub.2 O.sub.3 /(YO.sub.2 + WO + Z.sub.2 O.sub.5)                                               0.1 to 100                                                                               0.1 to 20                                       Solvent/            1 to 1500                                                                                 5 to 1000                                     (YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3)                           OH.sup.- /YO.sub.2                                                                                0 to 10     0 to 5                                        (M.sub.2/e O + R.sub.2/f O)/                                                                    0.01 to 20  0.05 to 5                                       (YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3)                           M.sub.2/e O/        0 to 10     0 to 5                                        (YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3)                           R.sub.2/f O/       0.1 to 20  0.12 to 1.0                                     (YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3)                           ______________________________________                                    

wherein e and f are the weighted average valences of M and R,respectively.

In this second method, when no Z and/or W oxides are added to thereaction mixture, the pH is important and must be maintained at fromabout 9 to about 14. When Z and/or W oxides are present in the reactionmixture, the pH is not narrowly important for crystallization of thepresent invention.

A third method for synthesis of the present crystalline material iswhere X comprises aluminum and Y comprises silicon, the crystallizationtemperature must be from about 25° C. to about 175° C., preferably fromabout 50° C. to about 150° C., and an organic directing agent,hereinafter more particularly described, or, preferably a combination ofthat organic directing agent plus an additional organic agent,hereinafter more particularly described, is used. This third methodcomprises preparing a reaction mixture containing sources of, forexample, alkali or alkaline earth metal (M), e.g. sodium or potassium,cation if desired, one or more sources of aluminum and/or silicon, anorganic (R) directing agent, hereinafter more particularly described,and a solvent or solvent mixture, such as, for example C₁ -C₆ alcohols,C₁ -C₆ diols and/or water, especially water, said reaction mixturehaving a composition, in terms of mole ratios of oxides, within thefollowing ranges:

    ______________________________________                                        Reactants       Useful      Preferred                                         ______________________________________                                        Al.sub.2 O.sub.3 /SiO.sub.2                                                                     0 to 0.5  0.001 to 0.5                                      Solvent/SiO.sub.2                                                                               1 to 1500    5 to 1000                                      OH.sup.- /SiO.sub.2                                                                             0 to 10      0 to 5                                         M.sub.2/e O + R.sub.2/f O)/                                                                   0.01 to 20   0.05 to 5                                        (SiO.sub.2 + Al.sub.2 O.sub.3)                                                M.sub.2/e O/      0 to 5       0 to 3                                         (SiO.sub.2 + Al.sub.2 O.sub.3)                                                R.sub.2/f O/    0.01 to 2    0.03 to 1                                        (SiO.sub.2 + Al.sub.2 O.sub.3)                                                ______________________________________                                    

wherein e and f are the weighted average valences of M and R,respectively.

In this third method, the pH is important and must be maintained at fromabout 9 to about 14. This method involves the following steps:

(1) Mix the organic (R) directing agent with the solvent or solventmixture such that the mole ratio of solvent/R_(2/f) O is within therange of from about 50 to about 800, preferably from about 50 to 500.This mixture constitutes the "primary template" for the synthesismethod.

(2) To the primary template mixture of step (1) add the sources ofoxides, e.g. silica and/or alumina such that the ratio of R_(2/f)O/(SiO₂ +Al₂ O₃) is within the range of from about 0.01 to about 2.0.

(3) Agitate the mixture resulting from step (2) at a temperature of fromabout 20° C. to about 40° C., preferably for from about 5 minutes toabout 3 hours.

(4) Allow the mixture to stand with or without agitation, preferably ata temperature of from about 20° C. to about 100° C., and preferably forfrom about 10 minutes to about 24 hours.

(5) Crystallize the product from step (4) at a temperature of from about50° C. to about 175° C., preferably for from about 1 hour to about 72hours. Crystallization temperatures higher in the given ranges are mostpreferred.

A fourth method for the present synthesis involves the reaction mixtureused for the third method, but the following specific procedure withtetraethylorthosilicate the source of silicon oxide:

(1) Mix the organic (R) directing agent with the solvent or solventmixture such that the mole ratio of solvent/R_(2/f) O is within therange of from about 50 to about 800, preferably from about 50 to 500.This mixture constitutes the "primary template" for the synthesismethod.

(2) Mix the primary template mixture of step (1) withtetraethylorthosilicate and a source of aluminum oxide, if desired, suchthat the R_(2/f) O/SiO₂ mole ratio is in the range of from about 0.5 toabout 2.0.

(3) Agitate the mixture resulting from step (2) for from about 10minutes to about 6 hours, preferably from about 30 minutes to about 2hours, at a temperature of from about 0° C. to about 25° C., and a pH ofless than 12. This step permits hydrolysis/polymerization to take placeand the resultant mixture will appear cloudy.

(4) Crystallize the product from step (3) at a temperature of from about25° C. to about 150° C., preferably from about 95° C. to about 110° C.,for from about 4 to about 72 hours, preferably from about 16 to about 48hours.

In each of the above methods, batch crystallization of the presentcrystalline material can be carried out under either static or agitated,e.g. stirred, conditions in a suitable reactor vessel, such as forexample, polypropylene jars or teflon lined or stainless steelautoclaves. Crystallization may also be conducted continuously insuitable equipment. The total useful range of temperatures forcrystallization is noted above for each method for a time sufficient forcrystallization to occur at the temperature used, e.g. from about 5minutes to about 14 days. Thereafter, the crystals are separated fromthe liquid and recovered.

When a source of silicon is used in the synthesis method, it ispreferred to use at least in part an organic silicate, such as, forexample, a quaternary ammonium silicate. Non-limiting examples of such asilicate include tetramethylammonium silicate andtetraethylorthosilicate.

Non-limiting examples of various combinations of W, X, Y and Zcontemplated for the first and second synthesis methods of the presentinvention include:

    ______________________________________                                        W        X              Y     Z                                               ______________________________________                                        --       Al             Si    --                                              --       Al             --    P                                               --       Al             Si    P                                               Co       Al             --    P                                               Co       Al             Si    P                                               --       --             Si    --                                              ______________________________________                                    

including the combinations of W being Mg, or an element selected fromthe divalent first row transition metals, e.g. Mn, Co and Fe; X being B,Ga or Fe; and Y being Ge.

An organic directing agent for use in each of the above methods forsynthesizing the present material from the respective reaction mixturesis an ammonium or phosphonium ion of the formula R₁ R₂ R₃ R₄ Q⁺, i.e.:##STR1## wherein Q is nitrogen or phosphorus and wherein at least one ofR₁, R₂, R₃ and R₄ is aryl or alkyl of from 6 to about 36 carbon atoms,e.g. --C₆ H₁₃, --C₁₀ H₂₁, --C₁₂ H₂₅, --C₁₄ H₂₉, --C₁₆ H₃₃ and --C₁₈ H₃₇,or combinations thereof, the remainder of R₁, R₂, R₃ and R₄ beingselected from the group consisting of hydrogen, alkyl of from 1 to 5carbon atoms and combinations thereof. The compound from which the aboveammonium or phosphonium ion is derived may be, for example, thehydroxide, halide, silicate, or mixtures thereof.

In the first and third methods above it is preferred to have anadditional organic directing agent and in the second method it isrequired to have a combination of the above organic directing agent anda additional organic directing agent. That additional organic directingagent is the ammonium or phosphonium ion of the above directing agentformula wherein R₁, R₂, R₃ and R₄ together or separately are selectedfrom the group consisting of hydrogen and alkyl of 1 to 5 carbon atomand combinations thereof. Any such combination of organic directingagents go to make up "R" and will be in molar ratio of about 100/1 toabout 0.01/1, first above listed organic directing agent/additionalorganic directing agent.

The particular effectiveness of the presently required directing agent,when compared with other such agents known to direct synthesis of one ormore other crystal structures, is believed due to its ability tofunction as a template in the above reaction mixture in the nucleationand growth of the desired ultra-large pore crystals with the limitationsdiscussed above. Non-limiting examples of these directing agents includecetyltrimethylammonium, cetyltrimethylphosphonium,octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium,myristyltrimethylammonium, dodecyltrimethylammonium anddimethyldidodecylammonium.

It should be realized that the reaction mixture components can besupplied by more than one source. The reaction mixture can be preparedeither batchwise or continuously. Crystal size and crystallization timeof the new crystalline material will vary with the nature of thereaction mixture employed and the crystallization conditions.

The crystals prepared by the instant invention can be shaped into a widevariety of particle sizes. Generally speaking, the particles can be inthe form of a powder, a granule, or a molded product, such as anextrudate having particle size sufficient to pass through a 2 mesh(Tyler) screen and be retained on a 400 mesh (Tyler) screen. In caseswhere the catalyst is molded, such as by extrusion, the crystals can beextruded before drying or partially dried and then extruded.

The present compositions are useful as catalyst components forcatalyzing the conversion of organic compounds, e.g. oxygenates andhydrocarbons, by acid-catalyzed reactions. The size of the pores is alsosuch that the spatiospecific selectivity with respect to transitionstate species is minimized in reactions such as cracking (Chen et al.,"Shape Selective Catalysts in Industrial Applications", 36 CHEMICALINDUSTRIES, pgs. 41-61 (1989) to which reference is made for adiscussion of the factors affecting shape selectivity). Diffusionallimitations are also minimized as a result of the very large pores inthe present materials. For these reasons, the present compositions areespecially useful for catalyzing reactions which occur in the presenceof acidic sites on the surface of the catalyst and which involvereactants, products or transitional state species which have largemolecular sizes, too great for undergoing similar reactions withconventional large pore size solid catalysts, for example, large poresize zeolites such as zeolite X, Y, L, ZSM-4, ZSM-18, and ZSM-20.

Thus, the present catalytic compositions will catalyze reactions such ascracking, and hydrocracking, and other conversion reactions usinghydrocarbon feeds of varying molecular sizes, but with particularapplicability to feeds with large molecular sizes such as highlyaromatic hydrocarbons with substituted or unsubstituted polycyclicaromatic components, bulky naphthionic compounds or highly substitutedcompounds with bulky steric configurations, e.g. molecular sizes ofabout 13 Angstroms or more. The present catalytic compositions areparticularly useful for reactions in which the molecular weight of thefeed is reduced to a lower value, i.e. to reactions involving crackingsuch as cracking or hydrocracking. Cracking may be conducted at atemperature of from about 200° C. to about 800° C., a pressure of fromabout atmospheric to about 100 psig and contact time of from about 0.1second to about 60 minutes. Hydrocracking may be conducted at atemperature of from about 150° C. to about 550° C., a pressure of fromabout 100 psig to about 3000 psig, and a weight hourly space velocity offrom about 0.1 hr⁻¹ to about 100 hr⁻ 1, with a hydrogen/hydrocarbonmolar ratio of from about 0.1 to about 100.

The catalytic compositions of matter according to the present inventionmay also be used for selective conversion of inorganic compounds such asoxides of nitrogen in mixtures of gases which contain nitrogen oxides(NO_(x)), for example, industrial exhaust gases and the gases formedduring the oxidative regeneration of catalysts used in the processing ofhydrocarbons, especially in catalytic cracking operations. The porouscrystalline material may be used in a matrixed or unmatrixed form forthis purpose and may suitably be formed into extrudates, pellets orother shapes to permit the passage of gases over the catalyst with theminimum pressure drop. The crystalline material is preferably at leastpartly in the hydrogen form, but it may advantageously contain a minoramount of noble metal as a catalytic component, especially a metal ofPeriods 5 and 6 Group VIIIA of the Periodic Table, especially platinum,palladium, ruthenium, rhodium, iridium or mixtures thereof. Amounts ofnoble metal up to about 1 weight percent are typical with lower amounts,e.g. up to about 0.1 or 0.5 weight percent being preferred.

The NO_(x) reduction is suitably conducted by passing the gas containingthe oxides of nitrogen over the catalyst at an elevated temperature,typically at least 200° C., and usually within the range of 200° to 600°C. The gas mixture may be mixed with ammonia to promote reduction of theoxides of nitrogen and pre-mixing may be conducted at a temperature ofup to about 200° C. The amount of ammonia which is mixed with the gasmixture is typically within the range of 0.75 to 1.25 the stoichiometricamount, which itself varies according to the ratio of the differentoxides of nitrogen in the gas mixture, as shown by the equations:

    6NO.sub.2 +8NH.sub.3 =7N.sub.2 +12H.sub.2 O

    6NO+4NH.sub.3 =5N.sub.2 +6H.sub.2 O

The crystalline catalytic compositions of matter may also be used forthe reduction of oxides of nitrogen in gaseous mixtures in the presenceof other reducing agents such as carbon or carbon monoxide. Reduction ofthe oxides of nitrogen in this way is of particular utility in theregeneration of fluid catalytic cracking (FCC) catalysts, sinceregeneration under appropriate conditions will produce the requiredconcentrations of carbon monoxide which may then be used to reduce theproportion of NO_(x) in the regeneration gases in the presence of thecatalyst.

Because the present catalytic compositions have been found to be stable,their use as cracking catalysts, e.g. in fluid catalytic crackingprocesses, with resid feeds will represent an especially favorable modeof utilization. Still further, they may be used in combination with oneor more other catalyst components such as, for example, crackingcatalysts comprising silica-alumina and/or zeolite Y, e.g. USY.

The present catalytic compositions are especially useful for reactionsusing high molecular weight, high boiling or non-distillable feeds,especially residual feeds, i.e. feeds which are essentiallynon-distillable or feeds which have an initial boiling point (5% point)above about 1050° F. Residual feeds which may be used with the presentcatalytic compositions include feeds with API gravities below about 20,usually below 15 and typically from 5 to 10 with Conradsen CarbonContents (CCR) of at least 1% by weight and more usually at least 5% ormore, e.g. 5-10%. In some resid fractions the CCR may be as high asabout 20 weight percent or even higher. The aromatic contents of thesefeeds will be correspondingly high, as may the contents of heteroatomssuch as sulfur and nitrogen, as well as metals. Aromatics content ofthese feeds will usually be at least 50 weight percent and typicallymuch higher, usually at least 70 or 80 weight percent, with the balancebeing principally naphthenes and heterocyclics. Typical petroleumrefinery feeds of this type include atmospheric and vacuum tower resids,asphalts, aromatic extracts from solvent extraction processes, e.g.phenol or furfural extraction, deasphalted oils, slop oils and residualfractions from various processes such as lube production, coking and thelike. High boiling fractions with which the present catalyticcompositions may be used include gas oils, such as atmospheric gas oils;vacuum gas oils; cycle oils, especially heavy cycle oil; deasphaltedoils; solvent extracts, such as bright stock; heavy gas oils, such ascoker heavy gas oils; and the like. The present catalytic material mayalso be utilized with feeds of non-petroleum origin, for example,synthetic oils produced by coal liquefaction, Fischer-Tropsch waxes andheavy fractions and other similar materials.

The compositions of this invention can also be used as adsorbents andseparation vehicles in pharmaceutical and fine chemical applications.For example, these ultra-large pore compositions may be used in thepurification of drugs like insulin or be used as solid vehicles for thecontrolled delivery of drugs. Another application for use of theseultra-large pore materials involves waste disposal where theextraordinary pore volumes are exploited. Therefore, at least onecomponent can be partially or substantially totally separated from amixture of components having differential sorption characteristics withrespect to the present ultra-large pore composition by contacting themixture with the composition to selectively sorb the one component.Examples of this include contacting a mixture comprising water and atleast one hydrocarbon component, whereby at least one hydrocarboncomponent is selectively sorbed. Another example includes selectivesorption of at least one hydrocarbon component from a mixture comprisingsame and at least one additional hydrocarbon component.

As in the case of many catalysts, it may be desired to incorporate thenew crystal composition with another material resistant to thetemperatures and other conditions employed in organic conversionprocesses. Such materials include active and inactive materials andsynthetic or naturally occurring zeolites as well as inorganic materialssuch as clays, silica and/or metal oxides such as alumina, titaniaand/or zirconia. The latter may be either naturally occurring or in theform of gelatinous precipitates or gels including mixtures of silica andmetal oxides. Use of a material in conjunction with the new crystal,i.e. combined therewith or present during synthesis of the new crystal,which is active, tends to change the conversion and/or selectivity ofthe catalyst in certain organic conversion processes. Inactive materialssuitably serve as diluents to control the amount of conversion in agiven process so that products can be obtained economically and orderlywithout employing other means for controlling the rate of reaction.These materials may be incorporated with naturally occurring clays, e.g.bentonite and kaolin, to improve the crush strength of the catalystunder commercial operating conditions. Said materials, i.e. clays,oxides, etc., function as binders for the catalyst. It is desirable toprovide a catalyst having good crush strength because in commercial useit is desirable to prevent the catalyst from breaking down intopowder-like materials. These clay binders have been employed normallyonly for the purpose of improving the crush strength of the catalyst.

Naturally occurring clays which can be composited with the new crystalinclude the montmorillonite and kaolin family, which families includethe subbentonites, and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dickite, nacrite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.

In addition to the foregoing materials, the new crystal can becomposited with a porous matrix such as silica-alumina, silica-magnesia,silica-zirconia, silica-thoria, silica-beryllia, silica-titania as wellas ternary compositions such as silica-alumina-thoria,silica-alumina-zirconia, silica-alumina-magnesia andsilica-magnesia-zirconia.

It may be desirable to provide at least a part of the foregoing matrixin colloidal form so as to facilitate extrusion of the bound catalystcomponents(s).

The relative proportions of finely divided crystalline material andinorganic oxide matrix vary widely, with the crystal content rangingfrom about 1 to about 90 percent by weight and more usually,particularly when the composite is prepared in the form of beads, in therange of about 2 to about 80 weight percent of the composite.

In order to more fully illustrate the nature of the invention and themanner of practicing same, the following examples are presented. In theexamples, whenever sorption data are set forth for comparison ofsorptive capacities for water, cyclohexane, benzene and/or n-hexane,they are Equilibrium Adsorption values determined as follows:

A weighed sample of the adsorbent, after calcination at about 540° C.for at least about 1 hour and other treatment, if necessary, to removeany pore blocking contaminants, is contacted with the desired pureadsorbate vapor in an adsorption chamber. The increase in weight of theadsorbent is calculated as the adsorption capacity of the sample interms of grams/100 grams adsorbent based on adsorbent weight aftercalcination at about 540° C. The present composition exhibits anequilibrium benzene adsorption capacity at 50 Torr and 25° C. of greaterthan about 15 grams/100 grams, particularly greater than about 17.5grams/100 grams and more particularly greater than about 20 grams/100grams.

A preferred way to do this is to contact the desired pure adsorbatevapor in an adsorption chamber evacuated to less than 1 mm at conditionsof 12 Torr of water vapor, 40 Torr of n-hexane or cyclohexane vapor, or50 Torr of benzene vapor, at 25° C. The pressure is kept constant(within about ±0.5 mm) by addition of adsorbate vapor controlled by amanostat during the adsorption period. As adsorbate is adsorbed by thenew crystal, the decrease in pressure causes the manostat to open avalve which admits more adsorbate vapor to the chamber to restore theabove control pressures. Sorption is complete when the pressure changeis not sufficient to activate the monostat.

Another way of doing this for benzene adsorption data is on a suitablethermogravimetric analysis system, such as a computer-controlled 990/951duPont TGA system. The adsorbent sample is dehydrated (physically sorbedwater removed) by heating at, for example, about 350° C. or 500° C. toconstant weight in flowing helium. If the sample is in as-synthesizedform, e.g. containing organic directing agents, it is calcined at about540° C. in air and held to constant weight instead of the previouslydescribed 350° C. or 500° C. treatment. Benzene adsorption isotherms aremeasured at 25° C. by blending a benzene saturated helium gas streamwith a pure helium gas stream in the proper proportions to obtain thedesired benzene partial pressure. The value of the adsorption at 50 Torrof benzene is taken from a plot of adsorption isotherm.

In the examples, percentages are be weight unless otherwise indicated.

EXAMPLE 1

Sodium aluminate (4.15 g) was added slowly into a solution containing 16g of myristyltrimethylammonium bromide (C₁₄ TMABr) in 100 g of water.Tetramethylammonium silicate (100 g), HiSil (25 G) andtetramethylammonium hydroxide (14.2 g) were then added to the mixture.The product was synthesized in a 600 cc autoclave at 120° C. withstirring for 24 hr.

The product was filtered, washed and air dried. Elemental analysisshowed the product contained 53.3 wt % SiO₂, 3.2 wt % Al₂ O₃, 15.0 wt %C, 1.88 wt %, N,0.11 wt % Na and 53.5 wt % ash at 1000° C. FIG. 1a showsthe x-ray diffraction pattern of the product calcined to 540° C. in N₂ 1hr and air for 6 hr.

EXAMPLE 2

A sample of the as-synthesized, washed product from Example 1 was washedwith hot water and then soaked in 0.25 M Na₂ CO₃ solution (50 cc/g) at80° C. for 1/2 hr. The product was filtered and washed. FIG. 1b showsthe x-ray diffraction pattern of the product calcined to 540° C. in N₂for 1 hr and air for 6 hr. The relative intensity of the broad peak(impurity phase) to the sharp peak at d=34.7 A (M41S) decreasedsignificantly after the treatment.

EXAMPLE 3

Sodium aluminate (4.15 g) was added slowly into a solution containing 46g of dodecyltrimethylammonium hydroxide (C₁₂ TMAOH, 50%) solutiondiluted with 120 g of water. Ludox (56.2 g) and tetramethylammoniumsilicate (100 g) and tetramethylammonium hydroxide (13.2 g) were thenadded to the mixture. The product was synthesized in a 600 cc autoclaveat 100° C. with stirring for 24 hr.

The product was filtered, washed and air dried. Elemental analysisshowed the product contained 51.0 wt % SiO₂, 3.4 wt % Al₂ O₃, 18.6 wt %C, 1.93 wt % N, 0.15 wt % Na and 54.3 wt % ash at 1000° C. FIG. 2a showsthe x-ray diffraction pattern of the as-synthesized, washed and airdried product.

EXAMPLE 4

A sample of the as-synthesized, washed product from Ex. 3 was washed andsoaked in 0.25M Na₂ CO₃ solution (50 cc/g) at 80° C. for 1/2 hr. Theproduct was filtered, washed and air dried. FIG. 2b shows the x-raydiffraction pattern of the carbonate treated, air dried product. Therelative intensity of the broad peak (impurity phase) to the sharp peakat d=34.3 A (M41S) decreased significantly after the treatment.

EXAMPLE 5

Sodium aluminate (8.3 g) was added slowly into a solution containing 92g of dodecyltrimethylammonium hydroxide (C₁₂ TMAOH) in 240 g of water.Tetramethylammonium silicate (200 g), HiSil (50 g) andtetramethylammonium hydroxide (26.4 g) were then added to the mixture.The mixture was crystallized in a 1 liter autoclave at 100° C. withstirring for 24 hr.

The product was filtered, washed and exchanged with 1N NH₄ NO₃ solutionfour times. FIG. 3a shows the x-ray diffraction pattern of the exchangedproduct calcined to 540° C. in N₂ for 1 hr and air for 6 hr. Thisproduct proved to have a surface area of 1109 m^(2/) g and anequilibrium adsorption capacity in g/100 g anhydrous benzene of 51. At427° C., WHSV=5, the product shows 6.2% ethylbenzene conversion.

EXAMPLE 6

A sample of the as-synthesized, washed product from Ex. 5 was washedwith hot water and then soaked in 0.25M Na₂ CO₃ solution (50 cc/g) at80° C. for 1/2 hr. The product was filtered, washed and then exchangedwith 1N NH₄ NO₃ solution four times. FIG. 3b shows the x-ray diffractionpattern of the treated, exchanged product calcined to 540° C. in N₂ for1 hr and air for 6 hr. The relative intensity of the broad peak(impurity phase) to the sharp peak at d=31.3 Å decreased significantlyafter the treatment.

This product proved to have a surface area of 1101 m² /g and aequilibrium adsorption capacity in g/100 g anhydrous benzene of 46.

EXAMPLE 7

The calcined product of Example 5 and the calcined, treated product ofExample 6 were used in the conversion of ethylbenzene at 427° C.,WHSV=5.

Table 1 summarizes the properties of the carbonate treated material ofExample 6 compared to the untreated material of Example 5.

                  TABLE 1                                                         ______________________________________                                                         Example 5                                                                             Example 6                                            ______________________________________                                        BET m.sup.2 /g     1109      1101                                             Benzene sorption, wt %                                                                           51        46                                               Ethylbenzene, Conv. wt %                                                                         6.2       9.8                                              ______________________________________                                    

What is claimed is:
 1. A method for purifying a composition of matterwhich comprises an inorganic, porous, non-layered crystalline phasematerial exhibiting, after calcination, an X-ray diffraction patternwith at least one peak at a d-spacing greater than about 18 AngstromUnits and having a benzene adsorption capacity of greater than 15 gramsbenzene per 100 grams of said material at 50 Torr and 25° C. andcontaining an impurity phase, the method comprising contacting thecomposition of matter, under conditions sufficient to solubilize theimpurity phase, with an aqueous solution which comprises a hydroxylconcentration sufficient to solubilize the impurity phase but not thecrystalline phase material.
 2. The method of claim 1 wherein thecomposition of matter comprises an inorganic, porous crystalline phasematerial having a hexagonal arrangement of uniformly-sized pores atleast about 13 Angstroms in diameter and exhibiting, after calcination,a hexagonal electron diffraction pattern that can be indexed with a d100value greater than 18 Angstrom Units.
 3. The method of claim 1 whereinthe composition of matter has a composition expressed as follows:

    M.sub.n/q (W.sub.a X.sub.b Y.sub.c Z.sub.d O.sub.h)

wherein M is one or more ions; n is the charge of the compositionexcluding M expressed as oxides; q is the weighted molar average valenceof M; n/q is the number of moles or mole fraction of M; W is one or moredivalent elements; X is one or more trivalent elements; Y is one or moretetravalent elements; Z is one or more pentavalent elements; a, b, c,and d are mole fractions of W, X, Y, and Z, respectively; h is a numberof from 1 to 2.5; and (a+b+c+d)=1.
 4. The method of claim 1 wherein thecomposition of matter has a composition on an anhydrous basis expressedas follows:

    rRM.sub.n/q (W.sub.a X.sub.b Y.sub.c Z.sub.d O.sub.h)

wherein R is the total organic material not included in M; r is thenumber of moles or mole fraction of R; M is one or more ions; n is thecharge of the composition excluding M espressed as oxides; q is theweighted molar average valence of M; n/q is the number of moles or molefraction of M; W is one or more divalent elements; X is one or moretrivalent elements; Y is one or more tetravalent elements; Z is one ormore pentavalent elements; a, b, c, and d are mole fractions of W, X, Y,and Z, respectively; h is a number of from 1 to 2.5; and (a+b+c+d)=1,wherein, when treated under conditions sufficient to remove R, saidcrystalline phase gives an X-ray diffraction pattern with at least onepeak at a position greater than about 18 Angstrom Units d-spacing andexhibits a benzene adsorption capacity of greater than about 15 gramsbenzene per 100 grams anhydrous crystal at 50 torr and 25° C.
 5. Themethod of claim 1 wherein the composition of matter comprises aninorganic, non-pillared crystalline phase giving an X-ray diffractionpattern following calcination with at least two peaks at positionsgreater than about 10 Angstrom Units d-spacing, at least one of which isat a position greater than about 18 Angstrom Units d-spacing, and nopeaks at positions less than about 10 Angstrom Units d-spacing withrelative intensity greater than about 20% of the strongest peak.
 6. Themethod of claim 1 wherein the aqueous solution comprises an alkali oralkaline earth metal carbonate with a pH greater than about
 8. 7. Themethod of claim 6 wherein the alkali or alkaline earth metal is selectedfrom a group consisting of lithium, rubidium, cesium, strontium, barium,sodium, potassium, calcium and magnesium.
 8. The method of claim 7wherein the carbonate comprises a molality of from about 0.001 to about1 M.
 9. The process of claim 2 wherein the aqueous solution comprises analkali or alkaline earth metal carbonate with a pH greater than about 8.10. The process of claim 9 wherein the alkali or alkaline earth metal isselected from a group consisting of lithium, rubidium, cesium,strontium, barium, sodium, potassium, calcium and magnesium.
 11. Themethod of claim 10 wherein the carbonate comprises a molality of fromabout 0.001 to about 1 M.
 12. A product of the method of claim
 1. 13. Aproduct of the method of claim
 2. 14. A product of the method of claim3.
 15. A product of the method of claim
 4. 16. A product of the methodof claim
 5. 17. A hydrocarbon conversion process comprising contacting ahydrocarbon feedstock with a composition of matter which comprises aporous, non-layered crystalline phase material exhibiting, aftercalcination, an x-ray diffraction pattern with at least one peak at ad-spacing greater than about 18 Angstrom Units and having a benzeneadsorption capacity greater than 15 grams benzene per 100 grams of saidmaterial at 50 torr and 25° C. and containing an impurity phase in anas-synthesized form, said composition of matter having been contactedwith an aqueous solution which comprises a hydroxyl concentrationsufficient to solubilize the impurity phase but not the crystallinephase material.
 18. The hydrocarbon conversion process of claim 17wherein the conversion process is an alkylation process.
 19. Thehydrocarbon conversion process of claim 18 wherein the alkylationprocess is an ethylbenzene conversion.